TW499467B

TW499467B - Coating compositions based on epoxy group-containing silanes

Info

Publication number: TW499467B
Application number: TW87114235A
Authority: TW
Inventors: Peter Bier; Herbert Krug; Stefan Sepeur; Sabine Stein
Original assignee: Bayer Ag; Inst Neue Mat Gemein Gmbh
Priority date: 1997-08-28
Filing date: 1998-08-28
Publication date: 2002-08-21
Also published as: CN1268966A; CN1162488C; KR20010023346A; AU9343198A; CA2302343A1; US6361868B1; IL134297A0; DE59802758D1; ID24485A; WO1999011725A1; KR100648575B1; ATE209237T1; DE19737475A1; JP2001514322A; AU739863B2; DK1012212T3; BR9812024A; EP1012212A1; ES2167940T3; EP1012212B1

Abstract

The present invention provides a coating composition which comprises at least one silicon compound (A) which has at least one radical which is bonded directly to Si, is not able to be separated hydrolytically and contains an epoxy group, a particulate material (B) which is selected from among oxides, oxide hydrates, nitrides and carbides of Si, Al and B and of transition metals and has a particle size within the range 1 to 100 nm, an Si, Ti, Zr, B, Sn or V compound (C) and at least one hydrolysable Ti, Zr or Al compound (D), which comprises the following ratio 1.0 mol of the silicon compound (A), 0.27 to 0.49 mol of the particulate material (B), 0.36 to 0.90 mol of the compound (C) and 0.14 to 0.22 mol of the compound (D).

Description

499467 A7 _——τ- -------------------- Β7 五、發明説明（1 ) " 一 ' — 本發明係冑關以含有環氧基之可水解石夕烧為底之塗料組合物、塗佈該塗料之物品及其用途。 ^適用為塗料之物質可由烷醇鹽類，例如：丙醇鋁或丁醇鋁，使用經改質之烷氧基矽烷，採用溶膠法製備。此等 /谷膠法實質上之特性為起始成份之混合物反應，因水解及縮合結果形成粘稠液相，此合成法產生之有機改質之無機母結構之表面硬度大於傳統之有機聚合物。然而，其重大缺點在於含鋁成份之高反應性阻礙了儲存期間（保存壽命）達到良好安定性。所得之薄層仍比無機材料軟。其原因為雖然物系中之無機成份產生了強烈交鏈效果，但其極小之大小仍阻礙如例如：硬度及耐磨性等機械性質發揮其效果。所謂的填充聚合物即有潛力完全發展出無機成份之有利之機械性質，因為其粒子大小為數個微米大。但在其透明方面仍有損失，以致無法再用於光學領域上。雖然可使用小Si〇2粒子（例如：Aerosils®)來生產提高耐磨性之透明薄層，但在可採用之低濃度下可達到之耐磨性數值仍舊與上述物系所達到之數值類似。可使用之填料品質之上限則由小粒子之高表面反應性決定，以致產生凝聚或無法接受之提高之粘度。 W0 95/13326說明一種製備經有機改質之無機系統，其硬度顯著高於上述物系，且透光度較高。其中亦說明適合保濩金屬表面防止腐餘之經有機改質之無機系統及用於親水性塗料之相關物系，該組合物之製法為在具有一個含烧氧基且直接與Si鍵結之至少一種預水解石夕化合物中添本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公^ "^^Α^ΒΑΥΙΝΜ) A7 2 選自Si、A1及β或過渡金屬之氧化物、氧化物水合物、硝化物及碳化物中之粒狀物質，其粒子大小範圍為1 至刚毫微米，以軟水!s石較佳，且/或添加非離子性界 ^活性劑及/或芳香系多元醇較佳。高度耐磨性係由預水解之矽化合物與粒狀物質組合所達成。另一方面，由預水解之矽化合物與界面活性劑組合，則形成親水性塗料，而由預水解之㈣合物與芳香系多元醇組合則得到抑制腐钱 =塗料。製造過程中可選擇添加氟化矽烷，以製得疏水性或ilL/由性塗料’或添加路易士鹼或醇鹽作為交鏈觸媒，或另添加可水解之化合物。 DE-4020 316-A1說明一種以可水解之矽烷為底之漆料，其硬化後提供耐磨之撓性塗層。其製法可由水與一種或多種含環氧基之矽化合物反應，其中水對可水解基團之莫耳比例為1:1至0·4··1。除了矽化合物外，亦可添加其他可水解化合物，例如：紹、鈦、錯、Μ、鍚、鐵及❿ 可在60C以上溫度使環氧基交鏈之第三胺特別適合作為使組合物硬化之觸媒。 DE-OS 30 21 018說明一種塗料組合物，其含有烷基三烷氧基矽烷、有機羧酸及陰離子性氟化碳界面活性劑之部份水解縮合產物。所使用之矽烷不含環氧基。該組合物提供之表面塗層具有耐磨表面，且具有良好透明度，耐熱性、及對基底材料之良好附著性，及防水性。 US-5 134 191說明一種硬性塗料組合物，其含有包含環氧基之有機矽化合物及微米以下之無機粒子，如··矽溶本紙張·尺度適州中國國家摞準（CNS ) Α4規格（2】0\297公^~ --------' 499467 A7 ____________—__B7 五、發明説明（3 ) "" 〜' 膠’且可使用最少量録化合物作為硬化觸媒進行硬化。豆適用為塑膠材料光學用品之塗層膜。該組合物亦可視需要包含一種紹化合物。本發明之目的為提供一種具有耐磨性、粘著性、塗漆雜及彈性之組合物’其甚至進—步改良，认前技藝組合物之膠凝及暗晦傾向低。此目的係由^種塗料組合物達成，其包含至少一種矽化合物（A)，其具有至少一個直接與Si鍵結、不會經水解分離且含有環氧基之自由基，粒狀物質（B)，其係選自： Si、A1與B及過渡金屬之氧化物、氧化物水合物’、、石肖化物及碳化物，其粒子大小在1至100毫微米之範圍内，一種 Si、Ti、Zr、B、Sri或V化合物⑹及至少一種可水解之 Ti、Zr、或A1化合物（D)，其特徵在於其所佔比例如下·· 1·〇莫耳矽化合物（A)，〇·27至〇·49莫耳粒狀物質（Β)， 0.36至0.90莫耳化合物（〇及〇· 14至0.22莫耳化合物（D)。根據本發明組合物之特徵為所使用組成份之某些定量比例’以產生對所塗佈之材料具有特別良好粘著性且顯著提高保存壽命之高度耐刮傷塗料。可另使用路易士鹼（Ε) 作為觸媒，以使本發明組合物更具親水性。可另使用具有至少一個含5至30個直接與碳原子鍵結之氟原子之不可水解自由基之可水解矽化合物（F)，其中後者之碳原子與Si間隔至少2個原子。採用這種氟化 m n (I m m n m m ϋ I A請先閱讀背面之注意事項再填寫本頁) 訂. 本纸張尺度適财® （CNS ) A4^ ( 210x297公釐7 499467 經沪部中决標率Χ;Ά,Τ·消於合作私印掣 A7 B7 五、發明説明（4 ) 矽烷時’可為相關之塗料賦予疏水性及防污性。為了達到持久之親水性，最好另使用非離子性界面活性劑（G)，及/或為了達到抑制腐蝕性質（提高對縮合作用之耐性），亦可另使用芳香系多元醇（H)。化合物（A)至（H)詳細說明如下：石夕化合物（A) 矽化合物（A)為具有可利用之2或3個（以3個較佳）可水解自由基，及1或2個（以1個較佳）不可水解自由基。單一不可水解自由基及二個不可水解自由基中至少一個分別具有一個可利用之環氧基。可水解自由基之實例為齒素（F、Cl、Br及I，特定吕之C1及Br)、烷氧基（特定言之&烷氧基，如，例如·甲氧基、乙氧基、正丙氧基、異丙氧基、及正丁氧，:異丁氧基、第二丁氧基及第三丁氧基）、芳氧基（特定言之芳氧基，例如：苯氧基）、醯氧基（特定言之 Cw醯氡基，如，例如··乙醯氧基與丙醯氧基）及烷羰基 (例如：乙醯基）。以烷氧基，特定言之甲氧基與乙氧基，為特別佳之可水解自由基。 _不含環氧基之不可水解自由基實例為氫、烷基，特定言之Cw烷基（如，例如：甲基、乙基、丙基及丁基）、烯土（特疋δ之C2·4烯基，如，例如：乙烯基、1 一丙烯基、2〜丙烯基及丁烯基）、炔基（特定言之G_4炔基，如例如·乙炔基及炔丙基）及芳基，特定言之芳基如，例如：苯基與萘基），其中前述基團可視需要含 (♦請先閱讀背面之注意事項再填寫本頁) 訂499467 A7 _—— τ- -------------------- B7 V. Description of the invention (1) " a '— The present invention is related to containing epoxy groups A hydrolyzable stone syrup-based coating composition, an article coated with the coating, and uses thereof. ^ Substances suitable for coatings can be prepared from alkoxides, such as aluminum propoxide or aluminum butoxide, using modified alkoxysilanes by the sol method. The essence of this / gluten method is the reaction of the mixture of the starting ingredients, which forms a viscous liquid phase as a result of hydrolysis and condensation. The surface hardness of the organically modified inorganic parent structure produced by this synthesis method is greater than that of traditional organic polymers. . However, its major disadvantage is that the high reactivity of the aluminum-containing ingredients prevents good stability during storage (shelf life). The resulting thin layer is still softer than the inorganic material. The reason is that although the inorganic component in the system has a strong cross-linking effect, its extremely small size still prevents mechanical properties such as hardness and wear resistance from exerting its effect. So-called filled polymers have the potential to fully develop the advantageous mechanical properties of inorganic components, as their particle size is several micrometers. However, there is still a loss in its transparency, so that it can no longer be used in the optical field. Although small Si02 particles (such as Aerosils®) can be used to produce transparent thin layers that improve wear resistance, the wear resistance values that can be achieved at the low concentrations that can be used are still similar to those achieved by the above systems . The upper limit of the quality of the fillers that can be used is determined by the high surface reactivity of the small particles, resulting in agglomeration or unacceptably increased viscosity. W0 95/13326 illustrates a method for preparing an organically modified inorganic system, the hardness of which is significantly higher than the above-mentioned systems, and the light transmittance is high. It also explains the organic modified inorganic system and related systems for hydrophilic coatings that are suitable for protecting metal surfaces from corrosion, and the composition is prepared by using a composition containing a thiol group and directly bonded to Si. At least one of the pre-hydrolyzed Shixi compounds is added to this paper in accordance with Chinese National Standard (CNS) A4 specifications (210X297) ^ " ^^ Α ^ ΒΑΥΙΝΜ) A7 2 selected from the group consisting of Si, A1, and β or transition metal oxides and oxidation Particulate matter in hydrates, nitrates, and carbides, with particle sizes ranging from 1 to just nanometers, soft water is preferred, and / or non-ionic active agents and / or aromatics are added Polyols are preferred. High abrasion resistance is achieved by a combination of pre-hydrolyzed silicon compounds and particulate matter. On the other hand, a combination of a pre-hydrolyzed silicon compound and a surfactant forms a hydrophilic coating, while a combination of a pre-hydrolyzed admixture and an aromatic polyol results in a corrosion-resistant coating. In the manufacturing process, it is optional to add fluorinated silane to obtain hydrophobic or ilL / free coatings' or to add Lewis base or alkoxide as a cross-linking catalyst, or to add a hydrolyzable compound. DE-4020 316-A1 describes a paint based on a hydrolyzable silane that hardens to provide a wear-resistant, flexible coating. It can be prepared by reacting water with one or more epoxy-containing silicon compounds, wherein the molar ratio of water to hydrolyzable groups is from 1: 1 to 0.4.1.1. In addition to silicon compounds, other hydrolyzable compounds can also be added, such as: Shao, Titanium, Cu, M, rhenium, iron, and rhenium. The third amine that can crosslink epoxy groups at temperatures above 60C is particularly suitable for hardening the composition. The catalyst. DE-OS 30 21 018 describes a coating composition comprising a partially hydrolyzed condensation product of an alkyltrialkoxysilane, an organic carboxylic acid, and an anionic fluorocarbon surfactant. The silane used does not contain epoxy groups. The surface coating provided by the composition has an abrasion-resistant surface, and has good transparency, heat resistance, good adhesion to a base material, and water resistance. US-5 134 191 describes a hard coating composition containing an organic silicon compound containing an epoxy group and inorganic particles below a micron, such as a silicon-soluble paper and a standard of China State Standards (CNS) Α4 specification ( 2】 0 \ 297 public ^ ~ -------- '499467 A7 ____________-__ B7 V. Description of the invention (3) " " ~' Glue 'and can use the minimum amount of recorded compounds as hardening catalyst for hardening Beans are suitable for coating films of optical materials of plastic materials. The composition may optionally include a compound. The purpose of the present invention is to provide a composition having abrasion resistance, adhesion, paint-painting and elasticity. Even further improvement, it is recognized that the pre-technical composition has a low tendency to gel and dull. This object is achieved by a coating composition containing at least one silicon compound (A), which has at least one directly bonded to Si 2, free radicals that do not separate by hydrolysis and contain epoxy groups, the granular substance (B), which is selected from the group consisting of: Si, A1 and B and oxides of transition metals, oxide hydrates', stone compounds and Carbides with a particle size of 1 to 100 millimeters Within the range of one meter, one Si, Ti, Zr, B, Sri or V compound ⑹ and at least one hydrolyzable Ti, Zr, or A1 compound (D) are characterized in that their proportions are as follows ... Ear silicon compound (A), 0.27 to 0.49 mole particles (B), 0.36 to 0.90 mole compounds (0 and 0.14 to 0.22 mole compound (D). According to the composition of the present invention It is characterized by certain quantitative proportions of the components used to produce highly scratch-resistant coatings that have particularly good adhesion to the material being coated and significantly increase the shelf life. Lewis base (E) can also be used as a catalyst In order to make the composition of the present invention more hydrophilic, a hydrolyzable silicon compound (F) having at least one non-hydrolyzable free radical containing 5 to 30 fluorine atoms directly bonded to carbon atoms may be additionally used, in which the carbon of the latter is Atoms are separated from Si by at least 2 atoms. Use this kind of fluorinated mn (I mmnmm 请 IA, please read the notes on the back before filling this page). 7 499467 The final bid rate of the Ministry of Economic Affairs of Shanghai; A7 B7 5. Description of the invention (4) In the case of silane, it can impart hydrophobicity and antifouling properties to related coatings. In order to achieve long-lasting hydrophilicity, it is best to use non-ionic surfactant (G), and / or Achieve corrosion inhibition properties (improve resistance to condensation), and aromatic polyols (H) can also be used. Compounds (A) to (H) are explained in detail as follows: Shixi compound (A) Silicon compound (A) has Available 2 or 3 (preferably 3) hydrolyzable free radicals and 1 or 2 (preferably 1) non-hydrolyzable free radical. A single non-hydrolyzable radical and at least one of the two non-hydrolyzable radicals each have an available epoxy group. Examples of hydrolyzable free radicals are halides (F, Cl, Br, and I, specific C1 and Br), alkoxy (specifically & alkoxy, such as, for example, · methoxy, ethoxy , N-propoxy, isopropoxy, and n-butoxy: isobutoxy, second butoxy, and third butoxy), aryloxy (specifically aryloxy, such as phenoxy Group), fluorenyloxy group (specifically, Cw fluorenyl group, such as, for example, ethenyloxy group and propionyloxy group), and alkylcarbonyl group (for example, ethenyl group). As the alkoxy group, specifically methoxy group and ethoxy group, hydrolyzable radicals are particularly preferable. _ Examples of non-hydrolyzable free radicals without epoxy groups are hydrogen, alkyl, specifically Cw alkyl (eg, methyl, ethyl, propyl, and butyl), allene (special C2 of δ 4 alkenyl, such as, for example, vinyl, 1-propenyl, 2 ~ propenyl, and butenyl), alkynyl (specifically G_4 alkynyl, such as, for example, ethynyl and propargyl), and aryl , Specific aryl groups such as, for example: phenyl and naphthyl, where the aforementioned groups can be included as required (♦ please read the precautions on the back before filling this page) Order

499467 A7 __ 五、發明説明（5 ^---〜有一個或多個取代基如，例如：鹵素及烧氧基。本文中亦可述及甲基丙稀丙基及甲基丙烯氧丙基。含有-個ί辰氧基之不可水解自由基實例特別指彼等具有可利用之甘油基或甘油氧基者。根據本發明可使用之矽化合物（Α)之具體實例可參見 ΕΡ-Α-195棚之第8及9頁，該案已併為本帽案之參考文獻。特別適合根據本發明之矽化合物（Α)為彼等如下通式者：499467 A7 __ 5. Description of the invention (5 ^ --- ~ There are one or more substituents such as, for example, halogen and alkoxy. Methyl propyl propyl and methacryloxy propyl can also be mentioned in this article Examples of non-hydrolyzable free radicals containing a hexanoyl group particularly refer to those having an available glyceryl group or glyceryloxy group. Specific examples of the silicon compound (A) that can be used according to the present invention can be found in EP-A- On pages 8 and 9 of Shed 195, this case has been incorporated as a reference to the hat case. Particularly suitable for the silicon compounds (A) according to the present invention are those of the following general formula:

RsSiR’ 其中R自由基相同或相異（最好相同），且代表可水解之基團（以Cw院氧基較佳，特定言之甲氧基及乙氧基），且R’代表甘油基-或甘油氧基—（Cl_2Q)伸烷基，特定言之β-甘油氧.乙基、γ-甘油丙基、δ-甘油氧丁基、ε-甘油氧戊基、ω-甘油氧己基、及2-(3,4-環氧環己基)-乙基-。以γ-甘油丙基三甲氧矽烷（下文簡稱GPTS)特別適用於本發明，因為其容易取得。粒狀物質（Β) 粒狀物質（Β)為Si、Α1及Β及過渡金屬（以Ti、Zr 及Ce較佳）之氧化物、氧化物水合物、硝化物或碳化物，其粒子大小在1至100毫微米之範圍内，以2至50 毫微米較佳，以5至20毫微米特別佳。此物質可使用之 -7- 本紙張尺度適州t國國家標準（CNS ) A4規格（210X297公釐） ----------Φ! 請先聞讀背面之注意事項再績寫本頁〕 •訂. A7 B7 1、發明説明（6 形式為粉末，然而最好呈轉形式（制）指經酸安定化者）較佳之粒狀物質為軟水Is、Ce〇2、Zr〇2及Ti〇2及石肖化鈦以毫微米大小之軟水!3石粒子特別佳。粒狀物質可自商品取得粉末形式，且由其製成（經酸安定化）溶膠之方法同樣係相關技藝已知者。此方面可進一步參考下文提供之製備實例制。利祕基丙酸安定毫微米大小之頌化鈦之原理已說明於例如：德國專利申請案p—43 34 639· 1 〇、 PH範圍在2·5至3·5 (以2·8至3·2較佳）之軟水鋁石/合膠特別適用，且可例如：由軟水鋁石粉末懸浮在稀HC1中製得。耄微米粒子之變化通常與相應材料之折射係數之變化有關。因此例如：以·或通粒子置換軟纽石粒子可使物質具有較高折射係數，根據勞倫茲—勞倫斯公式 (Lorentz-Lorenz equation)，其中之折射係數由高折射性成份及基質之體積加成決定。RsSiR 'wherein R radicals are the same or different (preferably the same), and represent hydrolyzable groups (Cw is preferably oxygen, specifically methoxy and ethoxy), and R' represents glyceryl -Or glyceryloxy- (Cl_2Q) alkylene, specifically β-glyceryloxy. Ethyl, γ-glycerylpropyl, δ-glyceryloxybutyl, ε-glyceryloxypentyl, ω-glyceryloxyhexyl, And 2- (3,4-epoxycyclohexyl) -ethyl-. Glycerylpropyltrimethoxysilane (hereinafter referred to as GPTS) is particularly suitable for the present invention because it is easily available. Particulate matter (B) Particulate matter (B) is an oxide, oxide hydrate, nitrate or carbide of Si, A1, and B and transition metals (preferably Ti, Zr, and Ce). In the range of 1 to 100 nm, 2 to 50 nm is preferable, and 5 to 20 nm is particularly preferable. This material can be used -7- This paper is compliant with National Standards (CNS) A4 specifications (210X297 mm) ---------- Φ! Please read the notes on the back before writing This page] • Order. A7 B7 1. Description of the invention (6 form is powder, but it is best to be in the form of conversion (manufactured) refers to those stabilized by acid) The preferred granular material is soft water Is, Ce〇2, Zr〇2 And Ti〇2 and Shi Xiaohua titanium soft water with nanometer size! 3 stone particles are particularly good. Particulate matter can be obtained in powder form from commercial products, and methods for making (acid-stabilized) sols from them are also known in the relevant art. In this regard, further reference may be made to the preparation examples provided below. The principle of rimidopropanoic acid for stabilizing nanometer-sized titanium oxide has been described in, for example, German patent application p-43 34 639 · 10, and the pH range is 2.5 to 3.5 (with 2.8 to 3 · 2 is preferred) boehmite / gum is particularly suitable, and can be prepared, for example, from boehmite powder suspended in dilute HC1. The change of 耄 micron particles is usually related to the change of the refractive index of the corresponding material. So for example: Substituting soft ornestone particles with · or through particles can make the material have a higher refractive index. According to the Lorentz-Lorenz equation, the refractive index is calculated by adding the highly refractive component and the volume of the matrix. Into a decision.

可水解化合物（CV 經济部中央榀牟而Μ工消资合作牡卬f ---------%——_ >(請先闡讀背面之注意事項再填寫本頁) 訂- 除了矽化合物（A)外，亦可使用選自下列元素之豆他可水解化合物：Si、Ti、Zr、M、B、Sn及V，其最好與石夕化合物（A)進行水解’以製備根據本發明組合物。化合物⑹為如下通式之Si、Ti、Zr、B、Sn及v化合物 R，R’4-x 或Hydrolysable compounds (CV Central Ministry of Economic Affairs, Ministry of Economic Affairs, Consumer and Industrial Cooperation, Cooperation----------% ----_ > (Please read the notes on the back before filling this page) Order- In addition to the silicon compound (A), other hydrolyzable compounds selected from the following elements: Si, Ti, Zr, M, B, Sn, and V, which are preferably hydrolyzed with the Shixi compound (A) 'to The composition according to the invention is prepared.Compound ⑹ is a compound R, R'4-x or Si, Ti, Zr, B, Sn and v of the following formula or

RxM^R^-x 499467 A7 B7 五、發明説明（7 ) 其中 Μ 代表 a) Si4+、Ti4+、Zn4+、Sn4+，或 b) Al3+、B3+或 (V0)3+，R代表可水解之自由基，R’代表不可水解之自由基，且若Μ為四價金屬原子（a項）時，X可為1至4，若 Μ為三價金屬原子（b項）時，X可為1至3。若化合物（c) 中含有數個自由基R及/或R’聘，其可相同或相異。X大於1較佳。亦即，化合物（c)具有至少一個可水解之自由基，以數個更佳。可水解自由基之實例為鹵素（F、Cl、Br及I，特定言之C1與Br)、烧氧基（特定言之Ci-4烧氧基，如，例如·· 甲氧基、乙氧基、正丙氧基、異丙氧基、及正丁氧基、異丁氧基、第二丁氧基或第三丁氧基）、芳氧基（特定言之 C6-H)芳氧基，例如··苯氧基）、醯氧基（特定言之Cl-4醯氧基，如，例如：乙醯氧基及丙醯氧基）及烷羰基（例如：乙醯基）。以烷氧基，特定言之甲氧基與乙氧基，為特別佳之可水解.，自由基。不可水解之自由基實例為氫、烧基，特定言之Cl-4烧基（如，例如：甲基、乙基、丙基與正丁基、異丁基、第二丁基及第三丁基）、烯基（特定言之C2-4烯基，如，例如：乙烯基、1-丙浠基、2-丙烯基及丁浠基）、炔基（特定言之C2-4炔基，如，例如：乙炔基及炔丙基）及芳基，特定言之，Cwo芳基，如，例如：苯基與萘基），其中前述基團視需要包含一個或多個取代基，如，例如：齒素及烷氧基。本文中亦可述及甲基丙烯丙基及甲基丙烯氡丙 -9- 本紙張尺度適/彳]中國國家標準（CNS ) Λ4規格（210X297公釐）請先W,讀背面之注意事項再填寫本頁、-ί·ν 499467 A7 B7 五、發明説明（8 ) (請先閲讀背一面，之注意事項再填寫本頁) 可使用之化合物（C)之具體實例如下，但其中不應因此限制任何適用之化合物（C)。RxM ^ R ^ -x 499467 A7 B7 V. Description of the invention (7) where M represents a) Si4 +, Ti4 +, Zn4 +, Sn4 +, or b) Al3 +, B3 + or (V0) 3+, R represents a hydrolyzable radical, R ′ represents a non-hydrolyzable radical, and if M is a tetravalent metal atom (item a), X may be 1 to 4, and if M is a trivalent metal atom (item b), X may be 1 to 3. If the compound (c) contains several radicals R and / or R ', they may be the same or different. X is preferably greater than 1. That is, the compound (c) has at least one hydrolyzable free group, more preferably several. Examples of hydrolyzable free radicals are halogens (F, Cl, Br and I, specifically C1 and Br), alkoxy (specifically Ci-4 alkoxy, such as, for example, methoxy, ethoxy Base, n-propoxy, isopropoxy, and n-butoxy, isobutoxy, second or third butoxy), aryloxy (specifically C6-H) aryloxy For example, phenoxy), fluorenyloxy (specifically, Cl-4 fluorenyloxy, such as, for example, ethynyloxy and propionyloxy), and alkylcarbonyl (for example, ethynyl). With alkoxy, specifically methoxy and ethoxy, especially hydrolyzable. Free radicals. Examples of non-hydrolyzable free radicals are hydrogen, alkyl, and specifically Cl-4 alkyl (eg, methyl, ethyl, propyl and n-butyl, isobutyl, second butyl, and third butyl) Group), alkenyl (specifically C2-4 alkenyl, such as, for example, vinyl, 1-propenyl, 2-propenyl, and butylfluorenyl), alkynyl (specifically C2-4 alkynyl, Such as, for example, ethynyl and propargyl) and aryl, and in particular, Cwo aryl, such as, for example, phenyl and naphthyl), wherein the aforementioned group optionally contains one or more substituents, such as, For example: tooth element and alkoxy. This paper can also refer to methacrylic propyl and methacrylic propylene -9- This paper is suitable in size / 彳] Chinese National Standard (CNS) Λ4 specification (210X297 mm) Please read W before reading the precautions on the back Fill out this page, ί · ν 499467 A7 B7 V. Description of the invention (8) (Please read the back of the page, the precautions before filling out this page) The specific examples of the compound (C) that can be used are as follows, but it should not be Restrict any applicable compound (C).

Si(OCH3)4, Si(OC2H5)4> Si(0-n- or i-C3H7)4,Si (OCH3) 4, Si (OC2H5) 4 > Si (0-n- or i-C3H7) 4,

Si(OC4H9)4, SiCl4, HSiCl3, Si(OOCCH3)4, CH3-S1CI3, CH3-Si(OC2H5)3> C2H5-SiCI3, C2H5-Si(OC2H5)3, C3H7-Si(OCH3)3, C6H5-Si(OCH3)3, CftH5-Si(OC2H5)3, (CH30)3-Si-C3H6-Gl, (CH3)2S1C12, (CH3)2Si(OCH3)2, (CH3)2Si(OC2H5)2, (CH5)2Si(OH)2, (C6H5)2SiCI2, (C6H5)2Si(OCH3)2, (C6H5)2Si(OC2H5)2, (i~C3H7)3SiOH, CH2=CH-Si(OOCCH3)3, CH2=CH-SiCI3, CH2=CH-Si(OCH3)3> CH2=CH-Si(OC2H5)3, CH2=CH-Si(OC2H4OCH3)3, CH2 = CH-CHrSi(OCH3)3， CH2=CH-CHrSi(OC2H5)3, CH2 = CH-CHrSi(OOCCH3)3， CH 尸 C(CH3)-COO-C3HrSi(OCH3)3， CH2=C(CH3)-COO-C3H7-Si(OC2H5)3， A1(0CH3)3, Al(OC2H5)3, Al(0-n-C3H7)3， ai(o小c3h7)3, Al(OC4H9)3, A1(CM-C4H9)3，Si (OC4H9) 4, SiCl4, HSiCl3, Si (OOCCH3) 4, CH3-S1CI3, CH3-Si (OC2H5) 3 > C2H5-SiCI3, C2H5-Si (OC2H5) 3, C3H7-Si (OCH3) 3, C6H5- Si (OCH3) 3, CftH5-Si (OC2H5) 3, (CH30) 3-Si-C3H6-Gl, (CH3) 2S1C12, (CH3) 2Si (OCH3) 2, (CH3) 2Si (OC2H5) 2, (CH5 ) 2Si (OH) 2, (C6H5) 2SiCI2, (C6H5) 2Si (OCH3) 2, (C6H5) 2Si (OC2H5) 2, (i ~ C3H7) 3SiOH, CH2 = CH-Si (OOCCH3) 3, CH2 = CH -SiCI3, CH2 = CH-Si (OCH3) 3> CH2 = CH-Si (OC2H5) 3, CH2 = CH-Si (OC2H4OCH3) 3, CH2 = CH-CHrSi (OCH3) 3, CH2 = CH-CHrSi (OC2H5 ) 3, CH2 = CH-CHrSi (OOCCH3) 3, CH (C3) -COO-C3HrSi (OCH3) 3, CH2 = C (CH3) -COO-C3H7-Si (OC2H5) 3, A1 (0CH3) 3 , Al (OC2H5) 3, Al (0-n-C3H7) 3, ai (osmall c3h7) 3, Al (OC4H9) 3, A1 (CM-C4H9) 3,

Al(0-jec-C4H9)3, AICI3, A1C1(0H)2, Al(OC2H4OC4H9)3,Al (0-jec-C4H9) 3, AICI3, A1C1 (0H) 2, Al (OC2H4OC4H9) 3,

Tick TKOC2HO4，Ti(0GH7)4，Tick TKOC2HO4, Ti (0GH7) 4,

Ti (0-i-C3H7)4, Ti (0C4H9)4, Ti (2-乙基己氧基）4 ;Ti (0-i-C3H7) 4, Ti (0C4H9) 4, Ti (2-ethylhexyloxy) 4;

Zrcl4, Zr(0C2H5)4, Zr(0C3H7)4, Zr(0-i~~C3H7)4, Zr(0C4H9)4， ZrOCh，Zr(2-乙基己氧基）4，及具有複合自由基之Zr化合物，如，例如：0-二酮自由基及曱基丙烯酸-自由基， ___ 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐）經浐部中夹樣舉而’、]1^.消轮合作私卬繁 499467 A7 ------------------------- B7 五、發明説明（9 ) BCk B(0CH3)3, B(〇C2H5)3，Zrcl4, Zr (0C2H5) 4, Zr (0C3H7) 4, Zr (0-i ~~ C3H7) 4, Zr (0C4H9) 4, ZrOCh, Zr (2-ethylhexyloxy) 4, and have complex free radicals Zr compounds, such as, for example, 0-diketone radicals and fluorenyl acrylic acid-radicals, ___ This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm). ] 1 ^ .Public cooperation in private round 499467 A7 ------------------------- B7 V. Description of invention (9) BCk B (0CH3) 3, B (〇C2H5) 3,

SnCk Sn(0CH3)4，SnCk Sn (0CH3) 4,

Sn(0C2H5)4 VOCh，ν〇_3)3〇以SiR4化合物特別適用，其中R自由基可相同或相異’且代表可水解基團，以含1至4個碳原子之烷氧基較佳，特定言之甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基或第三丁氧基。由此可見，此等化合物（c)(特定言之矽化合物）亦具有可利用之含C-C雙鍵或參鍵之不可水解自由基。若此等化合物與矽化合物（…共同使用（或甚至取而代之）時’組合物中亦可另含單體（以含環氧基或羥基者較佳）如’例如：甲基（丙烯酸酯）（此等單體當然亦可具有可利用之二個或多個相同型態之官能基，如，例如：有機多元醇之聚（甲基）丙烯駿酯；同樣可使用有機聚環氧化物）。當相應紕合物進行硬化時，則以加熱或光化學方式誘發，此時除了構成有機改質之無機基質外，尚由有機物進行聚合，導致相應塗層及模製體之交鏈密度提高，最後亦提高硬度。化合物（D) 化合物（D)為如下通式Ti、Zr或A1化合物較佳 M(R，，，）n -11- 本紙張尺度適W中國國家標準（CNS ) A4規格（210X297公釐）乂請先闖讀背面之注意事項再磧寫本頁) ΛΨ, 發明説明（10 ) /、中Μ代表Ti、Zr或A1，且自由基R，，,<相同或相異且代表可水解基團，且n為4 (㈣，Zr)或,Al)。Sn (0C2H5) 4 VOCh, ν〇_3) 3〇 is particularly suitable for SiR4 compounds, where the R radicals may be the same or different 'and represents a hydrolyzable group, compared with an alkoxy group containing 1 to 4 carbon atoms Preferably, specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy or third butoxy. It can be seen that these compounds (c) (specifically silicon compounds) also have non-hydrolyzable free radicals containing C-C double bonds or reference bonds. If these compounds are used together with silicon compounds (... or even replaced by them), the composition may also contain additional monomers (preferably those containing epoxy groups or hydroxyl groups) such as' for example: methyl (acrylate) ( These monomers may of course have two or more functional groups of the same type available, such as, for example, poly (meth) acrylic esters of organic polyols; organic polyepoxides may also be used). When the corresponding compound is hardened, it is induced by heating or photochemical methods. In this case, in addition to the organic matrix that constitutes the organic modification, organic compounds are also polymerized, resulting in an increase in the crosslink density of the corresponding coatings and molded bodies. Finally, the hardness is also increased. The compound (D) The compound (D) is a compound of the general formula Ti, Zr or A1, preferably M (R ,,,) n -11- The size of this paper is suitable for China National Standard (CNS) A4 specifications ( 210X297 mm) 乂 Please read the precautions on the back before writing this page) ΛΨ, Description of the Invention (10) /, where M stands for Ti, Zr or A1, and the radicals R ,,, < same or different And represents a hydrolyzable group, and n is 4 (㈣, Zr) or, Al)

可水解基團實例為鹵素（F、C1、阶及！，特定言之 Q及Br)、烷氧基（特定言之Ci e烷氧基，如，例如：甲氧基、乙氧基、正丙氧基、異丙氧基及正丁氧基、異丁氧第一丁氧基或第二T氧基、正戊氧基、正己氧基）、方氧基（特定言之C^o芳氧基，例如··苯氧基）、醯氧基 (特定言之Ch酿氧基，如，例如：乙醯氧基及丙醯氧基）及烧縣（例如：乙醯基）、或Ci6统氧基U 基，亦即衍生自基乙二醇H醇之基團，其中炫氧基與上述者相同。特別佳者，Μ為銘，且R，，，為乙醇鹽、第二丁醇鹽、正丙醇鹽或正丁氧乙醇鹽。發^易士鹼（Ε) 路易士驗⑻為氮化合物較佳，此等氮化合物可選 = :N-雜環、.含絲料、多環麵及氨（以水溶液佳）。其具體實例為卜甲基咪唾、2_(N，N_二甲「二:’㈣⑽-二甲胺甲基如及以-重氮雙 [5.4.0M-十-碳烯’其中以卜甲基輕特別佳。根^本制可❹之另―類含氮料錢為可水解具有至少-個包含至少—個第—、第基之不可水解自由基。此笪弟一解，且代表-種加較佳之含氮魏合物為彼c路易士驗 499467 A7 B7 、發明説明（nExamples of hydrolyzable groups are halogen (F, C1, order and !, specifically Q and Br), alkoxy (specifically Ci e alkoxy, such as, for example, methoxy, ethoxy, n- Propoxy, isopropoxy and n-butoxy, isobutoxy first butoxy or second Toxy, n-pentyloxy, n-hexyloxy), squareoxy (specifically C ^ o aromatic Oxygen, such as phenoxy), ethoxy (specifically Ch oxy, such as, for example, ethoxy and propionyl), and oxalic acid (such as: ethoxy), or Ci6 The oxy-U group, that is, the group derived from the ethylene glycol H alcohol, in which the oxo group is the same as the above. Particularly preferred, M is Ming, and R ,, is ethanolate, second butanolate, n-propanolate or n-butoxyethanolate. Fascia (E) Louise's test is preferably nitrogen compounds. These nitrogen compounds are optional:: N-heterocycles, silk-containing materials, polycyclic surfaces, and ammonia (preferably in aqueous solution). Specific examples thereof are buprofen, 2_ (N, N_dimethyl), bis: 'fluorene-dimethylamine methyl, and -diazobis [5.4.0M-deca-carbene', of which bumethyl is particularly preferable. Root ^ This system can be different-a kind of nitrogen-containing material is hydrolyzable with at least-containing at least-first-, non-hydrolyzable radicals. This brother has a solution, and represents-kind plus better Nitrogen-containing compounds are Louis C. 499467 A7 B7, invention description (n

RaSir 團h自由基相喊城（以相同較佳）且代表可水解基 (=α道氧基較佳’特定言之甲氧基與乙氧基），且 —代表與Si鍵結之不可水解自由基，其包含至少—個第二第二或第三胺基。此等頻之具體實例為3-胺丙基三 :孔傾、3-胺丙基三乙氧㈣、N_(2_胺乙基）_3_胺丙基，甲氧魏、N-[N’-(2’胺乙基)—2—胺乙基]_3_胺丙基三甲礼石夕院及N-[3-(三乙氧魏基）丙基]_4, 5_二氮味唾。 ^相應組合物中路易士鹼之一般用量為矽化合物（A)每 j耳環氧基制G.Gl i 0.5莫耳。較仙量為每莫耳環氧基使用0· 02至〇·3莫耳路易士驗，特定言之的〇· 1莫耳。含氟矽化合物（F) 經济部中夾ir:準^m,T.消抡合作私卬製 {請先閱•讀背面之注意事項再填寫本頁} ΤΧ» 尚可另外使用之可水解氟化矽烷（F)為彼等具有至少個含5至30個與碳原子鍵結之氟原子且該碳原子與^ 至少間隔2個原子之不可水解自由基者。此等矽烷詳述於 DE-OS 41 18 184。其具體實例如下： ' C2F5CHrCHrSiY3 n-C6F13CH2CHrSiY3 n-C8Fl7CH2CHrSiY3 n-Cl0F:ICH:CHrSiY5 (Y = OCH3, 〇C2H$ or Cl) i-C3F70-(CH2)3-SiCI:(CH3) n-C6F13CH2CH2SiCl2(CH3) n-C6Fl3CH2CH2SiCKCH3)2 13· 本紙張尺度適州中國國家標準（CNS ) A4規格（210X29*7公釐） 499467 A7 _____________—_____ B7__ 五、發明说明（12 ) 、請先閱讀背面之注意事項再填寫本頁此等氟化矽烷之一般用量佔組合物之0·1至15重量 %，以0· 2至10重量％較佳，且以0.5至5重量％特別佳。界面活性劑（G) 訂可用於達成持久抗暗晦效果且提高塗層親水性之界面活性劑（G)為非離子性界面活性劑較佳。以室溫下呈液態之非離子性界面活性劑特別佳。此等界面活性劑不僅可用在根據本發明組合物製法期間，而且亦可 (最好呈水溶液）在隨後利用熱擴散法，於約50至60°C 下添加。較佳界面活性劑為不同鏈長之聚氧乙嫦油基醚（例如：Brij®92，96或98，ICI公司）、不同鏈長之聚氧乙烯鯨蠟基醚（例如：Malipal®24/30至24/100，來自亨克公司（Henkel )之 Hiils nand Disponil ®〇5)、月桂基硫酸酯鈉（例如：亨克公司之suifopoI1 Spezial)、月桂基吡啶錆氣化物（例如：亨克公司之Dehydquad C Christ®)及聚氧乙烯山梨糖醇酐單油酸酯（例如：李達與海恩公司（Riedel andRaSir group h free radical phase (with the same preferred) and represents a hydrolyzable group (= α channel is better 'specifically methoxy and ethoxy), and-represents non-hydrolyzable with Si bond A free radical containing at least one second second or third amine group. Specific examples of these frequencies are 3-aminopropyltris: pore tilt, 3-aminopropyltriethoxyfluorene, N_ (2-aminoethyl) _3_aminopropyl, methoxycarb, N- [N ' -(2'Aminoethyl) -2-aminoethyl] _3-Aminopropyltrimethylstilite and N- [3- (triethoxyweilyl) propyl] _4,5_diazine. ^ The general amount of the Lewis base in the corresponding composition is 0.5 mole of G.Gl i made of silicon compound (A) per j earring oxygen. The relative amount is 0.02 to 0.3 Moore Lewis test per Mo earring oxygen, specifically 0.1 Moore. Fluorine-containing silicon compound (F) ir: quasi ^ m, T.Industrial cooperation and private system {please read and read the notes on the back before filling in this page} TX »Hydrolyzable fluorine that can be used separately Silanes (F) are those non-hydrolyzable free radicals which have at least 5 to 30 fluorine atoms bonded to carbon atoms, and the carbon atoms are separated by at least 2 atoms. These silanes are described in detail in DE-OS 41 18 184. The specific examples are as follows: 'C2F5CHrCHrSiY3 n-C6F13CH2CHrSiY3 n-C8Fl7CH2CHrSiY3 n-Cl0F: ICH: CHrSiY5 (Y = OCH3, 〇C2H $ or Cl) i-C3F70- (CH2) 3-SiCI: (CH3CH2CH3C2F3 ) n-C6Fl3CH2CH2SiCKCH3) 2 13 · The paper size is China State Standard (CNS) A4 size (210X29 * 7 mm) 499467 A7 __________________ B7__ 5. Description of the invention (12), please read the precautions on the back first Fill in this page The general amount of these fluorinated silanes is from 0.1 to 15% by weight of the composition, preferably from 0.2 to 10% by weight, and particularly preferably from 0.5 to 5% by weight. Surfactant (G) is a nonionic surfactant that can be used to achieve long-lasting anti-dull effect and improve the hydrophilicity of the coating. Nonionic surfactants which are liquid at room temperature are particularly preferred. These surfactants can be used not only during the preparation of the composition according to the present invention, but also (preferably in the form of an aqueous solution) and subsequently added at about 50 to 60 ° C using a thermal diffusion method. Preferred surfactants are polyoxyethyl oleyl ethers of different chain lengths (for example: Brij® 92, 96 or 98, ICI), polyoxyethylene cetyl ethers of different chain lengths (for example: Malipal® 24 / 30 to 24/100, Hiils nand Disponil ® 05 from Henkel, sodium lauryl sulfate (eg, suifopopo1 Spezial from Genk), laurylpyridine hydrazone (eg, Genk Dehydquad C Christ®) and polyoxyethylene sorbitan monooleate (for example: Riedel and Hein Company)

Haen )之 Tween® )。界面活性劑之一般用量佔塗料組合物〇1至35重量％。元醇（H) 根據本發明使用之芳香系多元醇之最大平均分子量為1000。此等多元醇實例為例如：於至少2個苯環上帶有經基之聚伸苯基醚，及其中芳香環利用單鍵、_ -14-Haen), Tween®). The surfactant is generally used in an amount of 0.01 to 35% by weight of the coating composition. Alcohol (H) The maximum average molecular weight of the aromatic polyol used according to the present invention is 1,000. Examples of these polyols are, for example: polyphenylene ether with a radical on at least two benzene rings, and the aromatic ring in which a single bond is used,

499467 A7 B7 五、發明説明（ 13 〇、—co s〇2—或類似鍵結互相鍵結且至少（爭好）含有2個羥基與芳香基键結之募聚物。特別佳之芳香系多元醇為芳香系二醇類特別佳代表為如下通式化合物：499467 A7 B7 V. Description of the invention (13 〇, —co s 02 — or similar bonds are mutually bonded and at least (competitively) agglomerates containing at least 2 hydroxyl groups and aromatic groups. A particularly preferred aromatic polyol Particularly preferred are aromatic diols represented by compounds of the following formula:

OH OH 其中X代表（C!-C8)伸烷基或—亞烷基、（Ce—Cl〇伸芳基、-〇 s C0-或-S〇2-且Π為0或1。X為G-C4伸烷基或-亞燒基，特定言之—C(CH3)2—，及_s〇2—較佳。化合物之芳香環除了-0H外，尚可帶有3或4個其他取代基，如，例如：商素、烷基及烷氧基。根據本發明可使用之芳香系多元醇（H)之具體實例為雙酚A、雙酚S及1,5-二羥基萘，以雙酚A較佳。多元醇CH)之一般用量為使矽化合物（A)之每莫耳環氧環含有0· 2至1.5莫耳芳香系多元醇（H)之羥基之量，以0· 3至1.2莫耳較佳，以0.6至1.0莫耳特別佳。根據本發明組合物中使用之矽化合物（A)具有至少二個可利用之環氧基，·使得所形成之塗層及模製體當曝露到縮合作用時，具有改善之安定性。根據本發明組合物之較佳製法更詳細說明於下文，其中由pH範圍在2· 5至3· 5 (以2· 8至3· 2較 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ 297公釐） ·(讀先閱讀背面之注意事項再填寫本頁} -訂經淨·部中夫榀率Ά 5消贽合作私卬製 499467 A7 —--------------------------- B 7 五、發明説明（14 ) ^ — 佳）之物質（B)之溶膠與其他成份之混合物反應。亦更佳之製法亦更詳細說明於下文中，其中由上述定義之溶膠分二部份加至⑷與（C)之混合物中，盆中最舰_某特定溫度，且射當在分兩次添加⑻ 之間添加（D)時，亦最好在某特定溫度下進行。根據本發明組合物中各組成份之用量應在指定之範圍内:在此前提條件τ，可得咖著改善耐到傷附著丨生塗漆枯度、膠凝時間、暗晦度及彈性之組合物。可水解之矽化合物（Α)可視需要與化合物〇使用酸觸媒（最好於室溫下），於水溶液中預水解，其中每莫耳可水解基團最好使用約1/2莫耳水。最好使用鹽酸作為預水解作用之觸媒。粒狀物質（Β)最好懸浮於水中，並調至ρΗ 2.5至 3，以2· 8至3· 2較佳。最好使用鹽酸酸化。若使用軟水I呂石作為粒狀物質（Β)時，則於此等條件下形成透明溶膠。由化合物（C)與化合物（Α)混合。然後添加第一份如上述之懸浮之粒狀物質（Β)。所選用之用量最好使其中所含之水量足以使化合物（Α)及（C)進行半化學計量性水解、此用量佔總用量之1〇至70重量％，以20至 50重量％較佳。添加後5分鐘，溶膠之溫度上升至約28至30°C，約20分鐘後，溶膠轉呈透明。混合物再搜拌約〇 5至 -16- 本、·氏張尺度4票準（CNS ) A4規格（2ι〇χ297公釐) " ,#請先閱讀背面之注意事項再填寫本Η ) 、v? Ί 1 I- I —I- I --- · 499467 A7 B7 經济部中央標卒而只Η消合作私卬％五、發明説明) 3小時，以1至2小時較佳。然後將整批溫度降至約〇 °C。然後添加化合物（D)，其中溫度不應超過約3〇c。化合物（D)添加完畢後，溶膠續於約〇°c下攪拌〇· 5至 3小時，以1至2小時較佳。然後添加其餘粒狀物質 (B)，其中溫度不應超過5°C。然後調整反應器溫度至 20°C，使組合物回升室溫。組合物保存在約4。〇之冰箱中。添加第一份物質（B)後，同樣在約〇〇c下，最好緩緩添加化合物（D)及可視需要選用之路易士鹼（E)。咸了解，室溫指20至23t之溫度。為了調整組合物之流動性質，可視需要在任何製備階段添加惰性溶劑。此等溶劑為室溫下呈液體之醇類較佳，且最好使用由烷醇鹽水解產生之醇類。特別佳之醇類為Cm醇類，特定言之曱醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三丁醇、正戊醇、異戊醇、正己酵"、正辛醇及正丁氧乙醇。CiB_二醇醚類，特定言之正丁氧乙醇同樣亦較佳。根據本發明組合物可另包含習知添加物如，例如··著色劑、流動促進劑、UV安定劑、光引發劑、感光劑（若需由組合物進行光化學硬化時）及熱聚合作用觸媒。在底材上之塗佈法為標準塗佈法，如，例如：浸泡、上色、刷拭、刀片塗佈法、滾轉法、喷洒法、帘幕式塗佈法、旋轉塗佈法及離心塗佈法。 (請先閱讀背面之注意事項再填寫本頁) d 訂 -17-OH OH where X represents (C! -C8) alkylene or -alkylene, (Ce-Cl0arylene, -0s CO- or -S〇2- and Π is 0 or 1. X is G -C4 alkylene or -alkylene, specifically -C (CH3) 2-, and _s〇2- are preferred. The aromatic ring of the compound may carry 3 or 4 other substitutions in addition to -0H. Groups such as, for example, quotients, alkyl groups, and alkoxy groups. Specific examples of the aromatic polyol (H) that can be used according to the present invention are bisphenol A, bisphenol S, and 1,5-dihydroxynaphthalene. Bisphenol A is preferred. The general amount of polyhydric alcohol CH) is such that the silicon compound (A) contains 0.2 to 1.5 moles of hydroxyl groups of the aromatic polyol (H) per mole of epoxy ring, with 0.3 It is more preferable to be 1.2 mol, especially 0.6 to 1.0 mol. The silicon compound (A) used in the composition according to the present invention has at least two available epoxy groups, so that the formed coating and molded body have improved stability when exposed to condensation. The preferred method of preparing the composition according to the present invention is described in more detail below, in which the pH range is from 2.5 to 3.5 (compared with 2.8 to 3.2). -15- This paper applies Chinese National Standard (CNS) A4 specifications (210 × 297 mm) · (Read the precautions on the back before filling out this page} -Booking net · Ministry and China's husband and wife rate 榀 5 Consumer cooperation private system 499467 A7 —------- -------------------- B 7 V. Description of the invention (14) ^ — good) The sol of substance (B) reacts with a mixture of other ingredients. It is also better The manufacturing method is also explained in more detail below, in which the sol as defined above is added to the mixture of ⑷ and (C) in two parts. The most specific temperature in the basin is between 温度 and ⑻. The addition of (D) is also preferably carried out at a certain temperature. The amount of each component in the composition according to the present invention should be within the specified range: under this prerequisite τ, it can be obtained to improve the resistance to wound adhesion 丨Raw paint dryness, gelation time, dullness and elasticity composition. Hydrolyzable silicon compound (A) can be used with compound 0 if necessary. Under temperature), it is pre-hydrolyzed in an aqueous solution. Among them, about 1/2 mol of water is preferably used per mole of hydrolyzable groups. Hydrochloric acid is preferably used as a catalyst for pre-hydrolysis. The particulate matter (B) is preferably suspended. In water and adjusted to ρΗ 2.5 to 3, preferably from 2 · 8 to 3 · 2. It is best to use hydrochloric acid for acidification. If soft water I lusite is used as the granular material (B), it is formed under these conditions Transparent sol. Mix compound (C) with compound (A). Then add the first part of suspended particulate matter (B) as described above. The amount used is preferably selected so that the amount of water contained in it is sufficient to make compound (A). And (C) performing semi-stoichiometric hydrolysis, this amount accounts for 10 to 70% by weight of the total amount, preferably 20 to 50% by weight. 5 minutes after the addition, the temperature of the sol rises to about 28 to 30 ° C, After about 20 minutes, the sol turns transparent. The mixture is then searched and mixed for about 0-5 to -16- this, Zhang's Zhang standard 4 votes standard (CNS) A4 size (2ι〇χ297 mm) ",#Please read the back first For the matters needing attention, fill in this again), v? Ί 1 I- I —I- I --- · 499467 A7 B7 Cooperation private Ang% V. invention is described) for 3 hours, preferably 1 to 2 hours. The entire batch temperature was then reduced to about 0 ° C. Compound (D) is then added where the temperature should not exceed about 30 ° C. After the addition of the compound (D), the sol is continuously stirred at about 0 ° C. for 0.5 to 3 hours, preferably 1 to 2 hours. Then add the remaining granular material (B), where the temperature should not exceed 5 ° C. The reactor temperature was then adjusted to 20 ° C to allow the composition to warm to room temperature. The composition is stored at about 4. 〇 in the refrigerator. After adding the first substance (B), it is also preferable to slowly add the compound (D) and the optional Lewis base (E) at about 0 ° C. It is understood that room temperature refers to a temperature of 20 to 23t. To adjust the flow properties of the composition, an inert solvent may be added at any stage of the preparation as needed. These solvents are preferably alcohols which are liquid at room temperature, and alcohols produced by the hydrolysis of alkanolates are preferred. Particularly preferred alcohols are Cm alcohols, specifically methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, n-pentanol, isoamyl alcohol, n-hexyl alcohol " , N-octanol and n-butoxyethanol. CiB_diol ethers, in particular n-butoxyethanol, are also preferred. The composition according to the present invention may further include conventional additives such as, for example, a colorant, a flow promoter, a UV stabilizer, a photoinitiator, a photosensitizer (if photochemical hardening is required from the composition), and thermal polymerization. catalyst. The coating method on the substrate is a standard coating method, such as, for example, dipping, coloring, brushing, blade coating method, roll method, spray method, curtain coating method, spin coating method, and Centrifugal coating method. (Please read the notes on the back before filling this page) d Order -17-

499467 A7 B7 五、發明説明（I6 ) 可視需要在表面先於室溫下乾燥後，再使塗佈之底材硬化。硬化過程最好於50至3〇(rc之溫度範圍内加熱，特疋§之70至200°C，且以90至18〇°C特別佳，可視需要在減塵下進行，在此等條件下之硬化時間短於200分鐘，以短於刚分鐘較佳，甚至短於6〇分鐘更佳。硬化層之層厚度應為〇·5至1〇〇微米，以Ί 至20微米較佳，特定言之2至1〇微米。若含有不飽和化合物及光引發劑時，亦可利用照射法進行硬化，然後可視需要進行加熱後硬化。塗佈用之底材材料沒有限制。根據本發明組合物較適於塗佈木材、織物、紙、石材、金屬、玻璃、陶質、及塑膠材料，且後者特別適合塗佈熱塑品，如述於貝克/布朗（Becker/Braun)之”塑膠學手冊（Kunststofftaschenbuch)(維也納、慕尼黑卡爾漢思出版社）（Carl Hanser Verlag)，1992。該組合物特別適合塗佈透明熱塑品，以聚碳酸酯較佳，或塗佈金屬或金屬化表面。特定言之眼鏡、光學鏡片、汽車窗及加熱頭可使用根據本發明得到之組合物塗佈。經浐部中决標準而消费合作扣印來下列實例進一步說明本發明：實例擾拌添加 129.04 克 Disperal Sol P3®至 1290.40 克〇· 1 N HC1中，以濃HC1調至pH 3，然後於室溫下攪拌14小時，再檢查pH —次。另外混合H81· 7克（5 莫耳）GPTS及625.0克（3莫耳）TE0S(四乙氧矽烷），並499467 A7 B7 5. Description of the invention (I6) If necessary, the surface is dried at room temperature before the coated substrate is hardened. The hardening process is preferably heated in the temperature range of 50 to 30 (rc), especially 70 to 200 ° C, and particularly preferably 90 to 180 ° C, and can be carried out under dust reduction if necessary. Under these conditions The lower hardening time is shorter than 200 minutes, preferably shorter than just 1 minute, and even better than 60 minutes. The layer thickness of the hardened layer should be 0.5 to 100 microns, preferably Ί to 20 microns. In particular, it is 2 to 10 microns. If unsaturated compounds and photoinitiators are contained, they can also be hardened by irradiation, and then can be hardened after heating if necessary. There is no limitation on the substrate material for coating. Combination according to the invention Materials are more suitable for coating wood, fabric, paper, stone, metal, glass, ceramic, and plastic materials, and the latter is particularly suitable for coating thermoplastics, as described in "Plastics" by Becker / Braun Handbook (Kunststofftaschenbuch) (Carl Hanser Verlag, Vienna, Munich), 1992. The composition is particularly suitable for coating transparent thermoplastics, preferably polycarbonate, or coating metal or metallized surfaces. Spectacles, optics Tablets, automotive windows, and heating heads can be coated with the composition obtained according to the present invention. The following examples are used to further illustrate the present invention through consumer cooperation deductions: Examples: Dispersal Sol Adds 129.04 grams of Disperal Sol P3® to 1294.40 In 0.1 g of HC1, adjust to pH 3 with concentrated HC1, and stir at room temperature for 14 hours, then check the pH. Repeat. Mix H81 · 7 g (5 mol) GPTS and 625.0 g (3 mol) ) TE0S (tetraethoxysilane), and

本紙張尺度適州中國國家標準（CNS ) A4規格（210X 297^^ ) ，__ A7 jt 二 ------------- ---B7 五、發明説明（17 ) 一—'~~ ----— 授摔10分鐘。以定量幫浦分配267.3克軟水链石溶膠 =此混合物中，流速為2〇克/分鐘。添加幾分鐘後， 4膠酿度上升至約28至3〇它，約20分鐘後，溶膠轉呈透月。混合物於室溫下攪拌約2小時，使溫度降至約0t。於〇cc±2t下，依約3毫升/分鐘之分配速率’添加378·54克（1莫耳）A1 (〇Et〇Bu)3。添加結束後、’於〇 c下攪拌2小時，再添加其餘軟水鋁石溶膠，同樣在約〇°C下，依約13毫升/分鐘之分配速率進行。所得反應混合物之溫度上升至室溫，不需控制溫度。添加Byk 306@作為流動促進劑，且在+4它下保持所得之漆料。根據本方法進行其他實例及對照實例，其中組成伤之用里係根據表1所示數值修改。採用所得之漆料，依下列方法得到試驗樣本：取以雙紛A為底之聚碳酸酯（玻璃態化溫度=147 C ’ ^27500)板，105x150x4毫米，以異丙醇清洗，浸入由3重量％胺丙基三甲氧矽烷與97重量％丁基二醇製備之混合物中，然後於l3(rc下加熱〇· 5小時，進行底漆塗佈。板子再於V=100公分/分鐘之浸泡速率下’塗佈20微米漆料層。於室溫下冷卻1〇分鐘後，塗好的板子於13(TC下乾燥1小時。乾燥後之漆料層厚度為約7微米。塗好的板子硬化後，於室溫下存放2 天，然後依下列方法測試。依下列方法測定此等漆料所得塗層之性質： -19- 本紙張尺度適州中國國家標準（CNS ) A4規格（210X297公釐）This paper is suitable for China National Standard (CNS) A4 specifications (210X 297 ^^), __ A7 jt II ------------- --- B7 V. Description of the invention (17) I- '~~ ----— 10 minutes of falling. 267.3 grams of soft water chain sol was dispensed with a quantitative pump = in this mixture, the flow rate was 20 grams / minute. After a few minutes of addition, the degree of gelation of the 4 gum rose to about 28 to 30 minutes, and after about 20 minutes, the sol turned into full moon. The mixture was stirred at room temperature for about 2 hours to reduce the temperature to about 0t. At 0cc ± 2t, 378.54 g (1 mole) of A1 (〇Et〇Bu) 3 was added at a dispensing rate of about 3 ml / min. After the addition was complete, '' was stirred at 0 ° C for 2 hours, and then the remaining boehmite sol was added, again at about 0 ° C, at a dispensing rate of about 13 ml / min. The temperature of the obtained reaction mixture was raised to room temperature, and no temperature control was required. Add Byk 306 @ as a flow promoter and keep the resulting paint at +4. Other examples and comparative examples were carried out according to this method, in which the composition of the wound was modified according to the values shown in Table 1. The obtained paint was used to obtain test samples according to the following methods: Take a polycarbonate (glass transition temperature = 147 C '^ 27500) plate with Shuangfan A as the base, 105x150x4 mm, clean with isopropanol, and immerse in In a mixture prepared by weight% aminopropyltrimethoxysilane and 97% by weight of butyl glycol, and then heated at 13 ° C for 0.5 hours to perform primer coating. The board was soaked at V = 100 cm / min. A 20 micron paint layer is applied at the rate. After cooling at room temperature for 10 minutes, the coated board is dried at 13 ° C for 1 hour. The thickness of the paint layer after drying is about 7 microns. The coated board After hardening, store at room temperature for 2 days, and then test according to the following methods. The properties of the coatings obtained from these paints are determined according to the following methods: -19- This paper is sized to China National Standard (CNS) A4 (210X297) %)

-----------*-----訂---；---- 6請先閲讀背面之注意事項再填寫本頁J 499467 A7 B7 五、發明説明（18 ) 網紋切割（gt)附著性試驗ΕΝ ISO 2409:1994保存於水（65°C)後，進行網紋切割附著性試驗後，tt (膠帶試驗）=0/1。塗漆的板子依EN ISO 2409:1994進行網紋切割試驗，並保存在65°C水中。所記錄之結果為膠帶試驗中首次損失附著性0至1時之保存時間（天數）。砂淋試驗·· DIN 52 348 塔柏（Taber)磨蝕機試驗：磨損試驗DIN 52 347 ; ( 1000 次循環，CS 10F，500 克）評估結果於下表： t請先閱，讀背面之注意事項再填寫本頁) -2 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 746949 r A7 B7 五、發明説明（19 ) I< 保存於水中後之網紋切割附著性試驗 (天數） DO Ό 寸 ο 網紋切割附著性試驗 (gt/tt) 〇〇 Ο δ ο δ i ο δ δ 砂淋試驗 4混濁度 (%) m «η m 〇· ο 塔柏磨蝕機試驗 Z混濁度 (%) __ __ _______ _ __ _ 寸〇6 οι MD r^t DO 寸 Al(〇EtOBu)3 '' (莫耳）〇 Ο ν〇 Ο 軟水鋁石 (莫耳） rv| 寸 οι ΓΟ ΟΙ οι TEOS (莫耳) 〇〇 rn ΟΊ r4 ΓΟ I 4.44 •r> m GPTS (莫耳） •η <〇，η 丨實例1 I <Ν m 革 % r-H CN 冢 ΓΟ (Κ .(請先朋讀背面之注意事項再填寫本頁訂本紙張尺度適州中國國家標準（CNS ) A4規格（210X297公釐）----------- * ----- Order ---; ---- 6 Please read the notes on the back before filling in this page J 499467 A7 B7 V. Description of Invention (18) Net Grain cutting (gt) adhesion test EN ISO 2409: 1994 After storing in water (65 ° C) and performing the web cutting adhesion test, tt (tape test) = 0/1. Lacquered boards were subjected to an anilox cutting test in accordance with EN ISO 2409: 1994 and stored in 65 ° C water. The recorded result is the storage time (days) when the adhesiveness was first lost in the tape test from 0 to 1. Sand test · DIN 52 348 Taber abrasion machine test: Wear test DIN 52 347; (1000 cycles, CS 10F, 500 g) The evaluation results are shown in the table below: tPlease read first, read the precautions on the back (Fill in this page again) -2 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 746949 r A7 B7 V. Description of the invention (19) I < Net texture cutting adhesion test after storage in water (days ) DO Ό Inch ο Mesh cutting adhesion test (gt / tt) 〇〇〇 δ ο δ i ο δ δ Sand test 4 Turbidity (%) m «η m 〇 · ο Taber Abraser Test Z Turbidity (%) __ __ _______ _ __ _ inch 〇6 οι MD r ^ t DO inch Al (〇EtOBu) 3 '' (Mole) 〇〇 ν〇〇 Boehmite (Mole) rv | inch οι ΓΟ ΟΙ οι TEOS (Mole) 〇〇rn 〇Ί r4 ΓΟ I 4.44 • r > m GPTS (Mole) • η < 〇, η Example 1 I < N m Leather% rH CN Read the notes on the back and fill in this page. The paper size is suitable for China National Standard (CNS) A4 (210X297 mm).

Claims

^^467六、申請專利範圍 A8 B8 C8 D8 -r 91 2, 專利申請案第87114235號 ROC Patent Appln. No.87114235 修正之申請專利範圍中文本—附件(一） Amended Claims in Chinese - Enci.(T) (民國91年2月4日送呈） (Submitted on February 4，2002) 1· 一種塗料組合物，其包含：至少一種矽化合物(Α)，其係為如下通式化合物： R3SiR，其中基團R為相同或相異，且代表Ci 4烷氧基，且R，代表甘油氧基-(CMG)伸烷基；一種粒狀物質⑼，其係為銘之氧化物或氧化物水合物，且其之粒子大小在1至1〇〇ηηι之範圍内；一種矽化合物(C)，其係為如下通式之化合物 (·請先閱讀背面之注意事項再填寫本頁) SiR, 經濟部智慧財產局員工消費合作社印製其中基團R為相同或不同，且代表Cm烧氧基及 ;以至少-種可搞之AHb合物(D)，其係為如下式化合物 A1R, 87316Β(9ΒΑΥΙΝΜ) 9〇· 11. 2,〇〇〇 -22 499467 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 D8 六、申請專利範圍其中基團R為相同或不同，且代表C1-6烷氧乙醇鹽基團；其特徵在於其佔之比例如下： 1.0莫耳矽化合物(A) 〇·27至〇·49莫耳粒狀物質(B) 〇·36至〇·90莫耳化合物(c)及〇·14至〇·22莫耳化合物(D)。 2·根據申請專利範圍第1項之組合物，其中(Α)為甘油氧丙基石夕烧，（B)為由粒子大小在1至100毫微米範圍内之軟水鋁石製備之溶膠，（C)為四乙氧矽烷，且〇3)為A1 (丁氧乙醇鹽）3。 3.根據申請專利範圍第丨或2項之組合物，其另包含路易士驗⑹及/或至少一種選自於c2F5CH2-CH2-SiY3、 n_C6F13CH2CH2-SiY3 、 n-C8F17CH2CH2-SiY3 、 n-C10F21CH2CH2-SiY3 、 i-C3F70-(CH2)-SiCl2(CH3)、 n-C6F13CH2CH2-SiCl2(CH3) 與 n-C6F13CH2CH2-SiCl(CH3)2，其中 γ 為〇ch3、〇C2H5 或 C卜中之可水解之矽化合物(F)，及/或界面活性劑(G)及 /或平均分子量不超過1000之芳香系多元醇出）。 4根據申請專利範圍第1項之組合物，其製法係由卩11在2.5 至3.5範圍中之粒狀物質(B)之溶膠與由矽化合物(A)及化合物(C) ’及化合物(D)與視需要選用之其他組成份(E)至 (H)製成之混合物反應。 5.根據申請專利範圍第4項之組合物，其製法係由石夕化合物 -23- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 90. 11. 2,000 I! ii—ίιί 訂！ ----線 1#------------ (在5«先閱讀背面之注意事項再填寫本頁) · 六、申請專利範圍 (A)與化合物(C)預混合，然後添加 (*請先閱讀背面之注意事項再填寫本頁) a) 第一份佔溶膠總量10至70重量％之pH在2.5至3.5 之物質(B)，然後添加 b) 化合物(D)，然後再添加 c) 第二份物質之溶膠。 6. 根據申請專利範圍第5項之組合物，其中步驟(a)之添加過程係在25°C以上進行，且步驟(b)之添加過程在0至3 °C下進行，步驟(c)在〇至5°C下進行。 7. 根據申請專利範圍第5或6項之組合物，其中化合物(A) 係視需要與化合物(c)使用HC1做為酸觸媒共同進行預水解。 8·根據申請專利範圍第5項之組合物，其中使用稀鹽酸來調整pH。 9.根據申請專利範圍第1項之組合物，其係用於塗佈任何型態底材材料。 10 ·根據申請專利範圍第9項之組合物，其中底材材料係為熱塑性塑料。 ^ 11.根據申請專利範圍第1項之組合物，其中底材材料係為聚經濟部智慧財產局員工消費合作社印製 12·根據申請專利範圍第9項之組合物，其中視需要調整流動性枭時，可在底材表面上塗佈含有惰性溶劑之組合物，且 (a)以加熱方式硬化，或(13)在先添加光引發劑之後，以一化學方式硬化，且視需要以加熱方式進行後硬化。光 13.根據中請專利範圍第12項之組合物，其中惰性溶劑係為 -24-^^ 467 VI. Application scope of patents A8 B8 C8 D8 -r 91 2, ROC Patent Appln. No. 87114235 with amendments to the scope of patent application Chinese text-Annex (I) Amended Claims in Chinese-Enci. T) (Submitted on February 4, 2002) 1. A coating composition comprising: at least one silicon compound (A), which is a compound of the general formula: R3SiR, where The group R is the same or different and represents Ci 4 alkoxy, and R represents glyceryloxy- (CMG) alkylene; a granular substance ⑼, which is an oxide or oxide hydrate of Ming, And its particle size is in the range of 1 to 100 nm; a silicon compound (C), which is a compound of the following formula (· Please read the precautions on the back before filling this page) SiR, Ministry of Economic Affairs Printed by the Consumer Cooperative of the Property Bureau where the groups R are the same or different and represent Cm oxy and Cm; and at least one of the available AHb compounds (D), which are compounds of the following formula A1R, 87316B (9BΑΥΙΝΜ) 9〇 · 11, 2,00〇-22 499467 Ministry of Economic Affairs Printed by A8, B8, C8, D8, Consumer Cooperatives of the Property Bureau 6. The scope of the patent application, where the groups R are the same or different, and represent C1-6 alkoxyethanol salt groups; its characteristics are as follows: 1.0 mole silicon Compound (A) 0.27 to 0.49 mole particles (B) 0.36 to 0.90 mole compound (c) and 0.14 to 0.22 mole compound (D). 2. The composition according to item 1 of the scope of the patent application, wherein (A) is glycerol oxypropyl spar, (B) is a sol prepared from boehmite having a particle size in the range of 1 to 100 nm, (C ) Is tetraethoxysilane, and 03) is A1 (butoxyethanol salt) 3. 3. The composition according to item 1 or 2 of the scope of patent application, which further comprises Louis test and / or at least one selected from c2F5CH2-CH2-SiY3, n_C6F13CH2CH2-SiY3, n-C8F17CH2CH2-SiY3, n-C10F21CH2CH2- SiY3, i-C3F70- (CH2) -SiCl2 (CH3), n-C6F13CH2CH2-SiCl2 (CH3) and n-C6F13CH2CH2-SiCl (CH3) 2, where γ is 〇ch3, 〇C2H5, or hydrolyzable in Cb Silicon compound (F), and / or surfactant (G) and / or aromatic polyol having an average molecular weight of not more than 1000). 4 The composition according to item 1 of the scope of patent application, which is prepared from sol of 卩 11 in the range of 2.5 to 3.5 of a granular substance (B) and silicon compound (A) and compound (C) 'and compound (D ) Reacts with a mixture made of other components (E) to (H) as required. 5. The composition according to item 4 of the scope of patent application, which is prepared by Shixi Compound-23- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 90. 11. 2,000 I! Ii — Ίιί Order! ---- 线 1 # ------------ (Read the precautions on the back before filling in this page at 5 «) 6. Scope of patent application (A) and compound (C) pre-mixed And then add (* Please read the notes on the back before filling this page) a) The first substance (B) with a pH of 2.5 to 3.5 which accounts for 10 to 70% by weight of the total sol, and then add b) Compound (D ), Then add c) a second part of the sol. 6. The composition according to item 5 of the scope of patent application, wherein the addition process of step (a) is performed above 25 ° C, and the addition process of step (b) is performed at 0 to 3 ° C, step (c) It is carried out at 0 to 5 ° C. 7. The composition according to item 5 or 6 of the scope of patent application, wherein the compound (A) is pre-hydrolyzed together with the compound (c) using HC1 as an acid catalyst if necessary. 8. A composition according to item 5 of the application, wherein dilute hydrochloric acid is used to adjust the pH. 9. The composition according to item 1 of the patent application scope, which is used for coating any type of substrate material. 10-The composition according to item 9 of the scope of patent application, wherein the substrate material is a thermoplastic. ^ 11. The composition according to item 1 of the scope of the patent application, where the substrate material is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs12. The composition according to the scope of the patent application, item 9, where the liquidity is adjusted as necessary For example, a composition containing an inert solvent may be coated on the surface of the substrate, and (a) is hardened by heating, or (13) after a photoinitiator is added first, it is hardened chemically, and if necessary, heated by heating Way for post-hardening. Light 13. The composition according to item 12 of the patent application, wherein the inert solvent is -24-

本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 499467 Α8 Β8 C8 D8 六、申請專利範圍正丁氧乙醇。 14·根據申請專利範圍第12項之組合物，其中組合物係於9〇至180°C之温度下硬化。 15·根據申请專利範圍第丨項之組合物，其係用於塗佈由金屬或玻璃或塑性材料所製得之物件。 16. 根據申請專利範圍第丨項之組合物，其係用於塗佈由聚碳酸酯所製得之物件。 17. 根據申睛專利範圍第丨項之組合物，其係用於塗佈鏡片、眼鏡、車窗或金屬加熱頭。 Γ 請先閱讀背面之注意事項再填寫本頁) 1%--訂 ί·-------線. 經濟部智慧財產局員工消費合作社印製 25 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 90. 11. 2,000The size of this paper applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 499467 Α8 Β8 C8 D8 6. Application scope of patent n-Butoxyethanol. 14. The composition according to item 12 of the scope of patent application, wherein the composition is hardened at a temperature of 90 to 180 ° C. 15. The composition according to item 丨 of the scope of patent application, which is used for coating objects made of metal or glass or plastic material. 16. The composition according to item 丨 of the scope of patent application, which is used for coating objects made of polycarbonate. 17. The composition according to item 丨 of the Shenyan patent scope, which is used for coating lenses, glasses, car windows or metal heating heads. Γ Please read the notes on the back before filling out this page) 1%-Order ί · ---------- line. Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 25 This paper size applies to Chinese National Standards (CNS) A4 size (210 X 297 mm) 90. 11. 2,000